US4364876A - Novel 2-cyanoacrylate, process for producing same and curable composition comprising same - Google Patents

Novel 2-cyanoacrylate, process for producing same and curable composition comprising same Download PDF

Info

Publication number
US4364876A
US4364876A US06/244,276 US24427681A US4364876A US 4364876 A US4364876 A US 4364876A US 24427681 A US24427681 A US 24427681A US 4364876 A US4364876 A US 4364876A
Authority
US
United States
Prior art keywords
cyanoacrylate
parts
ethoxyethyl
sub
methoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/244,276
Other languages
English (en)
Inventor
Kaoru Kimura
Kazuyuki Sakabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toagosei Co Ltd
Original Assignee
Toagosei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co Ltd filed Critical Toagosei Co Ltd
Assigned to TOAGOSEI CHEMICAL INDUSTRY CO., LTD. reassignment TOAGOSEI CHEMICAL INDUSTRY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KIMURA KAORU, SAKABE KAZUYUKI
Application granted granted Critical
Publication of US4364876A publication Critical patent/US4364876A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • This invention relates to a novel 2-cyanoacrylate, a process for producing the same and a curable composition comprising it.
  • alkyl 2-cyanoacrylate monomers have widely been utilized for bonding metals, plastics, rubbers, wood, ceramics and the like as a cold-setting one-pack type instant-setting adhesive anion-polymerizable with the very small quantity of water adsorbed on the surface of an adherend.
  • Improving the flexibility of cured product of an adhesive by changing the kind of the alcohol moiety of 2-cyanoacrylate can be predicted from the case of alkyl acrylate polymer. That is, it is known that the higher the alcohol moiety of the alkyl acrylate, the more flexible the polymer formed becomes, and the most flexible polymer among the alkyl acrylate polymers is an n-octyl acrylate polymer. If this idea is applied to alkyl 2-cyanoacrylates to investigate the properties of higher alkyl 2-cyanoacrylate polymers, they are not flexible polymers but rather brittle polymers.
  • the alkyl 2-cyanoacrylate polymers are polymers of 1,1-disubstituted vinyl compounds and the substituents thereof are a nitrile group and a carboxyl group, both having a very high polarity, the polymers are very rigid, linear polymers and it is inferred that a mere introduction of a higher alkyl group into the side chain of the polymer cannot render the polymer flexible.
  • the polymer is used as a paint, a coating material, a resist, a binder or the like.
  • the present inventors have conducted extensive research on a modification of such conventional rigid 2-cyanoacrylates to obtain a flexible cured product. As a result, they have succeeded in obtaining a 2-cyanoacrylate which can be cured to give a flexible product, by introducing a group having an affinity to the main chain structure of the cured product of 2-cyanoacrylate which is a rigid, 1,1-disubstituted vinyl polymer and having a plasticizing effect, into the side chain of the polymer.
  • a 2-cyanoacrylate represented by the formula (I): ##STR2## wherein R 1 is a 1,2-alkylene group having 2-4 carbon atoms, R 2 is an alkylene group having 2-4 carbon atoms and R 3 is an alkyl group having 1-6 carbon atoms.
  • a curable composition comprising a stabilizer and the 2-cyanoacrylate represented by the above-mentioned formula (I) or a mixture of said 2-cyanoacrylate and other 2-cyanoacrylate monomer represented by the formula (II): ##STR3## wherein R 4 is an alkyl group having 1-12 carbon atoms, an alkenyl group, an alkinyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxyalkyl group; said alkyl, alkenyl, alkinyl, cycloalkyl, aryl and aralkyl groups may optionally have a halogen substituent or an ether linkage; and said alkoxyalkyl group may have a halogen substituent.
  • Examples of the group R 4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, methoxyethyl, ethoxyethyl, butyloxyethyl, methoxypropyl, methoxybutyl, tetrahydrofurfuryl, allyl, propargyl, cyclohexyl, benzyl, 2-chlorethyl, trifluorethyl and the like.
  • 2-cyanoacrylate monomer all the usually known 2-cyanoacrylates may be used.
  • the curable composition of this invention When it is intended that the curable composition of this invention be cured by anionic polymerization with moisture, it can serve as an adhesive. When it is intended that an anion-polymerization initiator or a radical polymerization initiator be allowed to be present in the composition, the composition can be applied as paints, various coating materials and molding materials.
  • 2-cyanoacrylates have been produced by reacting a cyanoacetate with formaldehyde in the presence of a basic catalyst such as a secondary amine, a sodium alkoxide or the like to prepare a condensate having a degree of condensation of 5-50, and thermally depolymerizing the condensate at 150°-200° C. in the presence of P 2 O 5 or the like.
  • a basic catalyst such as a secondary amine, a sodium alkoxide or the like
  • the novel 2-cyanoacrylate represented by the formula (I) of this invention can also be produced by a processs similar to the hitherto known one.
  • the cyanoacetate used in this invention as a starting material is obtained by esterification of cyanoacetic acid with an alcohol or by transesterification between an alkyl cyanoacetate and an alcohol, as shown in the following schemes: ##STR5##
  • Examples of the alcohol represented by HO--R 1 --O--R 2 --O--R 3 used in this invention include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl ether, dibutylene glycol monomethyl ether, dibutylene glycol monoethyl ether, dibutylene glycol monobutyl ether, mono(3-methoxypropyl)-ethylene glycol, mono(3-methoxybutyl)-ethylene glycol, mono(3-methoxypropyl)-propylene-1,2-gly
  • a cyanoacetate of the above-mentioned alcohol and formaldehyde or paraformaldehyde are condensed in the presence of a catalyst at a molar ratio of 0.5-1.5:1, preferably 0.8-1.2:1, to obtain a condensate.
  • the catalyst is a base or an amine such as piperidine, diethylamine, dibutylamine, morpholine, KOH, NaOH, sodium alkoxide, secondary amine salt or the like, which is used in an amount of 0.001-10 mole%, preferably 0.01-1 mole%, based on the cyanoacetate.
  • the solvent for the reaction there may be used benzene, toluene, xylene, trichloroethylene, methylchloroform, tetrahydrofuran, ethanol, butanol, water or the like.
  • benzene, toluene, xylene, trichloroethylene, methylchloroform, tetrahydrofuran, ethanol, butanol, water or the like When the reaction is carried out at a temperature of 20°-150° C., preferably 50°-130° C., a condensate having a degree of condensation of about 5-50 is obtained with formation of condensation water.
  • this condensation reaction mixture is depolymerized either directly or after removal of the condensation catalyst.
  • the depolymerization is carried out at a reaction temperature of 140°-250° C. at a pressure of 0.1-50 mmHg in the presence of 0.01-10% by weight of phosphorus pentoxide, phosphoric acid, condensed phosphoric acid or the like.
  • the crude cyanoacrylate formed by the depolymerization reaction is again distilled, whereby the cyanoacrylate of this invention having a high purity is obtained.
  • the novel 2-cyanoacrylate of this invention thus obtained is a monomer having a high purity and a low or medium viscosity which is represented by the formula (I).
  • the 2-cyanoacrylate of this invention is a novel compound which can be anion-polymerized with a slight quantity of water, an amine, an alkali or the like or can be radical-polymerized with a peroxide or an azo compound similarly to the hitherto known alkyl 2-cyanoacrylates.
  • the novel 2-cyanoacrylate represented by the formula (I) of this invention has two ether linkages (--C--O--C--) in the alcohol moiety of the ester and is characterized in that the alkylene group (R 1 of formula (I)) to which the 2-cyanoacryloyl group is directly bonded in an ethylene group, a propylene group or a butylene group connected to the adjacent ether linkage at the 1,2-position.
  • Such a 2-cyanoacrylate is easy to synthesize, high in purity, excellent in storage stability and very effective as an adhesive.
  • 2-cyanoacrylates wherein R 2 of the formula (I) is an alkylene group having 2-4 carbon atoms (in this case, the alkylene group may be 1,2-, 1,3- or 1,4-one) and R 3 of the formula (I) is an alkyl group having 1-6 carbon atoms are preferred.
  • the novel 2-cyanoacrylate represented by the formula (I) of this invention is used to form a curable composition which is used as an adhesive or the like, at least one member selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenol, Bisphenol A, anisole, 2,6-di-t-butylphenol (BHT), sulfurous acid (SO 2 ), p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, carbon dioxide gas, thionyl chloride, propane sultone and the like is added as a stabilizer in an amount of 1-10,000 ppm (by weight) and preferably 10-1,000 ppm (by weight).
  • an adhesive having the desired viscosity can be obtained by dissolving a polymer such as alkyl acrylate polymer, for example, polyalkyl acrylates and copolymers of alkyl acrylate and vinyl acetate, styrene, butadiene, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, glycidyl methacrylate and the like; alkyl methacrylate polymer, for example, polyalkyl methacrylates and copolymers of alkyl methacrylate and vinyl acetate, styrene, butadiene, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, glycidyl methacrylate, and the like; alkyl cyanoacrylate polymer; acetylcellulose, polystyrene or the like into the composition.
  • a polymer such as alkyl acrylate polymer, for example, polyalkyl acrylates
  • a plasticizer may be added if it is necessary.
  • a flexible cured product can be obtained by adding dioctyl phthalate, dibutyl phthalate, trioctyl trimellitate, dioctyl adipate, dioctyl glutarate or the like in an amount of 0-50% by weight based on the weight of the 2-cyanoacrylate.
  • fine particles of, for example, silica, alumina, silica-alumina, boron nitride, polyethylene, Teflon or the like may be added as a filler to improve the bonding strength and adhesion.
  • a fine particle having a size of 0.001-100 ⁇ is added in an amount of 1-30% by weight based on the weight of the 2-cyanoacrylate.
  • a dye or a pigment may be added sometimes.
  • a perfume may also be added for the sake of aromatization.
  • an adhesive in the form of a curable composition comprising the 2-cyanoacrylate of the formula (I) of this invention
  • it is anion-polymerized and cured by the slight quantity of water adsorbed on said surface similarly to the hitherto known alkyl 2-cyanoacrylates, to effect bonding.
  • this adhesive gives a very flexible cured adhesive so that it is effective for bonding flexible materials such as leather, vinyl sheet, rubber, fiber, paper and the like. That is, there is an advantage that the cured adhesive and the neighborhood of the bonded part become as flexible as the bonded material.
  • a hitherto known 2-cyanoacrylate represented by the formula (II) may be added to the 2-cyanoacrylate of this invention represented by the formula (I) to improve the strength.
  • a higher blending ratio of the novel 2-cyanoacrylate (I) of this invention gives a higher flexibility
  • a higher blending ratio of the hitherto known 2-cyanoacrylate (II) gives a higher hardness to the cured product.
  • the blending ratio of the novel 2-cyanoacrylate (I) of this invention to the hitherto known 2-cyanoacrylate (II) is in the range of 1-100:99-0, preferably 30-100:70-0 by weight.
  • the novel 2-cyanoacrylate (I) of this invention or its mixture with a hitherto known 2-cyanoacrylate (II) is anion-polymerized by a slight quantity of water.
  • it can also be anion-polymerized by a base or a weak base such as amines, alkalis, phosphines, sulfides, mercaptans, quaternary ammonium salts, water, alcohols or the like to form a polymer having the following skeleton: ##STR7##
  • a base or a weak base such as amines, alkalis, phosphines, sulfides, mercaptans, quaternary ammonium salts, water, alcohols or the like.
  • a base or a weak base such as amines, alkalis, phosphines, sulfides, mercaptans, quaternary ammonium salts, water, alcohols or the like.
  • N,N-dimethylaniline, N,N-dimethyl-p-toluidine, sodium ethoxide, triethylbenzylammonium chloride and the like are particularly effective.
  • novel 2-cyanoacrylate (I) of this invention is radical-polymerized with a radical initiator, a cured product having the same skeleton as above is obtained.
  • a radical initiator peroxides and azo compounds such as benzoyl peroxide, azobisisobutyronitrile and the like are effective for the radical polymerization of this invention.
  • a photosensitizer such as benzophenone, benzoin monomethyl ether or the like facilitates the photopolymerization.
  • novel 2-cyanoacrylate (I) of this invention can also be radical-copolymerized with almost all kinds of vinyl monomers.
  • the curable composition of this invention comprising the novel 2-cyanoacrylate is useful not only as an adhesive but also as a paint and various coating materials. It can also be used as a molding material or a potting material.
  • the homopolymer and copolymers of the 2-cyanoacrylate of this invention are also applicable to paints, various coating materials, resists, binders, and the like.
  • ABS/ABS 5 seconds
  • This monomer was anion-polymerized with N,N-dimethyl-p-toluidine to obtain a polymer.
  • the polymer was transparent and had a flexible nature. Its glass transition temperature (Tg) was -5° C.
  • ethyl 2-cyanoacrylate was anion-polymerized in the same manner as above to obtain a cured product. It was hard and had a T g of 100° C. Further, a cured product of n-hexyl 2-cyanoacrylate was also examined. It was hard and brittle.
  • the 2-(2'-ethoxy)-ethoxyethyl-2"-cyanoacrylate (I) obtained in Example 2 was mixed with ethyl 2-cyanoacrylate (II) in a proportion as shown in Table 2, and 50 ppm of sulfurous acid gas and 1,000 ppm of hydroquinone were added thereto to prepare an adhesive. The bonding performances of the adhesives were measured to obtain the results shown in Table 2.
  • Neoprene rubber was selected as a flexible material. Two pieces of neoprene rubber were bonded to each other with a 2-cyanoacrylate adhesive as shown in Table 3 and the tensile shear strength of bond was measured according to JIS K 6861-1977. The results obtained were as shown in Table 3.
  • Test piece neoprene rubber: 3 ⁇ 25 ⁇ 100 mm
  • Bonding conditions 23 ⁇ 1° C., 60 ⁇ 2% RH, aging for 24 hours.
  • An adhesive obtained by adding 50 ppm of SO 2 thereto had a setting time of 45 seconds on rigid polyvinyl chloride and gave a flexible cured product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US06/244,276 1980-03-27 1981-03-16 Novel 2-cyanoacrylate, process for producing same and curable composition comprising same Expired - Lifetime US4364876A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3817480A JPS56135455A (en) 1980-03-27 1980-03-27 Novel 2-cyanoacrylate and curable composition
JP55-38174 1980-03-27

Publications (1)

Publication Number Publication Date
US4364876A true US4364876A (en) 1982-12-21

Family

ID=12518014

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/244,276 Expired - Lifetime US4364876A (en) 1980-03-27 1981-03-16 Novel 2-cyanoacrylate, process for producing same and curable composition comprising same

Country Status (8)

Country Link
US (1) US4364876A (Direct)
JP (1) JPS56135455A (Direct)
CA (1) CA1161062A (Direct)
DE (1) DE3111974A1 (Direct)
FR (1) FR2479208B1 (Direct)
GB (1) GB2073183B (Direct)
IE (1) IE51033B1 (Direct)
MX (1) MX157722A (Direct)

Cited By (110)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675270A (en) * 1986-02-10 1987-06-23 Loctite (Ireland) Limited Imaging method for vapor deposited photoresists of anionically polymerizable monomer
US4986884A (en) * 1986-11-08 1991-01-22 Bayer Aktiengesellschaft Process for the production of monomeric α-cyanoacrylates
US5244968A (en) * 1987-03-19 1993-09-14 The Dow Chemical Company Aqueous-dispersed polymer compositions containing cyanoalkyl esters of unsaturated carboxylic acids
US5262200A (en) * 1992-03-27 1993-11-16 Alan Puder System and method of applying cyanoacrylate adhesive activator
US5328687A (en) * 1993-03-31 1994-07-12 Tri-Point Medical L.P. Biocompatible monomer and polymer compositions
US5624669A (en) * 1993-03-31 1997-04-29 Tri-Point Medical Corporation Method of hemostatic sealing of blood vessels and internal organs
US5877230A (en) * 1991-11-12 1999-03-02 University Of Georgia Research Foundation, Inc. Anionic photoinitiation
US5928611A (en) * 1995-06-07 1999-07-27 Closure Medical Corporation Impregnated applicator tip
US6010714A (en) * 1996-11-22 2000-01-04 Closure Medical Corporation Non-thermogenic heat dissipating biomedical adhesive compositions
US6143805A (en) * 1998-02-18 2000-11-07 Closure Medical Corporation Electron beam sterilization of liquid adhesive compositions
US6143352A (en) * 1994-06-28 2000-11-07 Closure Medical Corporation pH-modified biocompatible monomer and polymer compositions
US6174919B1 (en) 1998-02-18 2001-01-16 Closure Medical Corporation Cyanoacrylate compositions with vinyl terminated ester groups
US6183593B1 (en) 1999-12-23 2001-02-06 Closure Medical Corporation 1,1-disubstituted ethylene adhesive compositions containing polydimethylsiloxane
US6217603B1 (en) 1997-08-29 2001-04-17 Closure Medical Corporation Methods of applying monomeric compositions effective as wound closure devices
US6245933B1 (en) 1999-11-19 2001-06-12 Closure Medical Corporation Transesterification method for making cyanoacrylates
US6283933B1 (en) 1998-12-23 2001-09-04 Closure Medical Corporation Applicator for dispensable liquids
US6310166B1 (en) 1999-08-12 2001-10-30 Closure Medical Corporation Sterilized cyanoacrylate solutions containing thickeners
US6323275B2 (en) 1992-05-28 2001-11-27 Toagosei Co., Ltd. Cyanoacrylate adhesive composition
US20020018689A1 (en) * 1995-06-07 2002-02-14 Badejo Ibraheem T. Adhesive applicators with improved polymerization initiators
US6352704B1 (en) 1999-06-30 2002-03-05 Closure Medical Corporation Flavored cyanoacrylate compositions
WO2002053666A1 (en) * 2001-01-08 2002-07-11 Loctite (R & D) Limited Cyanoacrylate compositions curable to flexible polymeric materials
US6425704B2 (en) 2000-01-07 2002-07-30 Closure Medical Corporation Adhesive applicators with improved applicator tips
US6428234B1 (en) 2000-01-07 2002-08-06 Closure Medical Corporation Adhesive applicator tips with improved flow properties
US6428233B1 (en) 2000-01-07 2002-08-06 Closure Medical Corporation Adhesive applicator tips with improved flow properties
US6433036B1 (en) 1997-02-27 2002-08-13 Loctite Corporation Radiation-curable, cyanoacrylate-containing compositions
US6455064B1 (en) 1998-04-30 2002-09-24 Closure Medical Corporation Method of applying an adhesive composition over a bioactive polymerization initiator or accelerator
US6512023B1 (en) 1998-06-18 2003-01-28 Closure Medical Corporation Stabilized monomer adhesive compositions
US20030063944A1 (en) * 1995-06-07 2003-04-03 Closure Medical Corporation Impregnated applicator tip
US6547467B2 (en) 2001-08-29 2003-04-15 Closure Medical Corporation Microapplicators, delivery systems and methods for adhesives and sealants
US6595940B1 (en) 1998-12-23 2003-07-22 Closure Medical Corporation Applicator for dispensable liquids
US6605667B1 (en) 2000-09-08 2003-08-12 Closure Medical Corporation Antioxidant enriched adhesive compositions and storage containers therefor
US6607631B1 (en) 2000-09-08 2003-08-19 Closure Medical Corporation Adhesive compositions with reduced coefficient of friction
US6616019B2 (en) 2001-07-18 2003-09-09 Closure Medical Corporation Adhesive applicator with improved applicator tip
US6660327B2 (en) 2001-12-28 2003-12-09 Mattel, Inc. Process of applying a cyanoadhesive composition
US6748950B2 (en) 2001-04-30 2004-06-15 Closure Medical Corporation Compositions and medical procedure to treat snoring
US20040137067A1 (en) * 1998-04-30 2004-07-15 Closure Medical Corporation Adhesive applicator tip with a polymerization initiator, polymerization rate modifier, and/or bioactive material
US20040151688A1 (en) * 2003-01-31 2004-08-05 Closure Medical Corporation Adhesive treatment for epistaxis
US6779657B2 (en) 2001-06-06 2004-08-24 Closure Medical Corporation Single-use applicators, dispensers and methods for polymerizable monomer compound
US6811341B2 (en) 2001-08-16 2004-11-02 Closure Medical Corporation Multiple-component combining
US20040223946A1 (en) * 2003-05-05 2004-11-11 Closure Medical Corporation Adhesive treatment for insect and related bites
US20040223932A1 (en) * 2003-05-05 2004-11-11 Closure Medical Corporation Adhesive treatment for acne
US20050042266A1 (en) * 2003-08-21 2005-02-24 Closure Medical Corporation Cyanoacrylate compositions containing anti-microbial agent
US20050042197A1 (en) * 1998-11-12 2005-02-24 Shalaby Shalaby W. Stabilized polyester/cyanoacrylate tissue adhesive formulation
US20050182443A1 (en) * 2004-02-18 2005-08-18 Closure Medical Corporation Adhesive-containing wound closure device and method
US6977278B1 (en) 2001-01-08 2005-12-20 Loctite (R&D) Ltd. Cyanoacrylate compositions curable to flexible polymeric materials
US20060009099A1 (en) * 2004-07-12 2006-01-12 Closure Medical Corporation Adhesive-containing wound closure device and method
US20070078207A1 (en) * 2005-09-30 2007-04-05 Jonn Jerry Y Stabilizer cyanoacrylate formulations
US20070213553A1 (en) * 2006-03-10 2007-09-13 Hongbo Liu Method for producing a cyanoacrylate monomer
US20080003196A1 (en) * 2006-06-30 2008-01-03 Jonn Jerry Y Absorbable cyanoacrylate compositions
WO2008067220A2 (en) 2006-11-30 2008-06-05 Closure Medical Corporation Dispenser
US7569719B1 (en) 2006-10-25 2009-08-04 Loctite (R&D) Limited Method of preparing electron deficient olefins
US20090203934A1 (en) * 2006-10-25 2009-08-13 Loctite (R&D) Limited Novel iminium salts and methods of preparing electron deficient olefins using such novel iminium salts
EP2116126A1 (en) 2008-05-06 2009-11-11 Henkel AG & Co. KGaA Method and apparatus for grafting plants with fast-curing adhesives
US20100030258A1 (en) * 2008-07-31 2010-02-04 Badejo Ibraheem T Controlled Exotherm of Cyanoacrylate Formulations
US7659423B1 (en) 2006-04-18 2010-02-09 Loctite (R&D) Limited Method of preparing electron deficient olefins in polar solvents
US20100047433A1 (en) * 2006-10-06 2010-02-25 Toagosei Co., Ltd Polymer for detecting fingerprint, method of producing the same, composition for detecting fingerprint and method of detecting fingerprint using the same
US7718821B1 (en) 2006-12-19 2010-05-18 Loctite (R&D) Limited Method of preparing electron deficient olefins
US20100199888A1 (en) * 2007-10-24 2010-08-12 Loctite (R&D) Limited Activated methylene reagents and curable compositions prepared therefrom
US20100210788A1 (en) * 2007-10-24 2010-08-19 Loctite (R&D) Limited Electron deficient olefins
US20100330027A1 (en) * 2009-06-30 2010-12-30 Hongbo Liu Cyanoacrylate Initiator System
US7932305B2 (en) 2008-06-27 2011-04-26 Ethicon, Inc. Viscous α-cyanoacrylate compositions
US7973119B1 (en) 2007-10-24 2011-07-05 Loctite (R&D) Limited Adhesive systems using imines and salts thereof and precursurs to electron deficient olefins
EP2363209A2 (en) 2003-02-07 2011-09-07 Ethicon, Inc. Applicators, dispensers and methods for dispensing and applying adhesive material
US20110230561A1 (en) * 2008-11-25 2011-09-22 Hongbo Liu Medical adhesive compositions
US8053589B1 (en) 2007-10-24 2011-11-08 Henkel Ireland Limited Imines and methods of preparing electron deficient olefins using such novel imines
US8198344B2 (en) 2008-06-20 2012-06-12 Adhezion Biomedical, Llc Method of preparing adhesive compositions for medical use: single additive as both the thickening agent and the accelerator
US8293838B2 (en) 2008-06-20 2012-10-23 Adhezion Biomedical, Llc Stable and sterile tissue adhesive composition with a controlled high viscosity
US8337881B2 (en) 2003-09-08 2012-12-25 Ethicon, Inc. Cyanoacrylate monomer formulation containing diiodomethyl-p-tolylsulfone
WO2013028672A1 (en) 2011-08-25 2013-02-28 Ethicon, Inc. Protective wound dressing device for oral and pharyngeal space
US8399698B1 (en) 2008-10-24 2013-03-19 Henkel Ireland Limited Substituted activated methylene reagents and methods of using such reagents to form electron deficient olefins
CN103232366A (zh) * 2013-04-25 2013-08-07 华南理工大学 一种α-氰基丙烯酸-2-甲氧基乙酯的制备方法
US8609128B2 (en) 2008-10-31 2013-12-17 Adhezion Biomedical, Llc Cyanoacrylate-based liquid microbial sealant drape
US8613952B2 (en) 2007-11-14 2013-12-24 Adhezion Biomedical, Llc Cyanoacrylate tissue adhesives
US8652510B2 (en) 2008-10-31 2014-02-18 Adhezion Biomedical, Llc Sterilized liquid compositions of cyanoacrylate monomer mixtures
US8729121B2 (en) 2007-06-25 2014-05-20 Adhezion Biomedical, Llc Curing accelerator and method of making
US8790032B2 (en) 2003-02-07 2014-07-29 Ethicon, Inc. Applicators, dispensers and methods for dispensing and applying adhesive material
WO2014172519A1 (en) 2013-04-19 2014-10-23 Adhezion Biomedical, Llc Package system for sterilizing and storing cyanoacrylate adhesive compositions
US9018254B2 (en) 2007-06-25 2015-04-28 Adhezion Biomedical, Llc Cyanoacrylate tissue adhesives with desirable permeability and tensile strength
US9254133B2 (en) 2008-10-31 2016-02-09 Adhezion Biomedical, Llc Sterilized liquid compositions of cyanoacrylate monomer mixtures
EP2995663A1 (en) 2014-09-12 2016-03-16 Afinitica Technologies, S. L. Fast and elastic adhesive
US9309019B2 (en) 2010-05-21 2016-04-12 Adhezion Biomedical, Llc Low dose gamma sterilization of liquid adhesives
US9421297B2 (en) 2014-04-02 2016-08-23 Adhezion Biomedical, Llc Sterilized compositions of cyanoacrylate monomers and naphthoquinone 2,3-oxides
US9528034B2 (en) 2013-05-21 2016-12-27 Henkel IP & Holding GmbH Cyanoacrylate compositions
US9839717B2 (en) 2015-09-10 2017-12-12 Fa-Ter CHU Cyanoacrylate adhesive composition and method for making the same
WO2018114460A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
WO2018114457A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefin precursors
WO2018114464A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
WO2018114458A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
WO2018114463A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefin precursors
USD824525S1 (en) 2014-09-25 2018-07-31 Ethicon Llc Release paper for wound treament devices
WO2018148057A1 (en) 2017-02-07 2018-08-16 Adhezion Biomedical, Llc Packaging for adhesive compositions, method for sterilizing
WO2018148453A1 (en) 2017-02-09 2018-08-16 Femasys, Inc. Methods and compositions comprising biodegradable cyanoacrylates
US10196316B2 (en) 2013-12-05 2019-02-05 Toagosei Co., Ltd. Reinforcement method for three-dimensional shaped object
US10196471B1 (en) 2008-10-24 2019-02-05 Henkel IP & Holding GmbH Curable composition having an electron deficient olefin
US10470935B2 (en) 2017-03-23 2019-11-12 Ethicon, Inc. Skin closure systems and devices of improved flexibility and stretchability for bendable joints
US10470934B2 (en) 2016-09-29 2019-11-12 Ethicon, Inc. Methods and devices for skin closure
US10687986B2 (en) 2016-09-29 2020-06-23 Ethicon, Inc. Methods and devices for skin closure
US10792024B2 (en) 2016-09-28 2020-10-06 Ethicon, Inc. Scaffolds with channels for joining layers of tissue at discrete points
WO2020212585A1 (en) 2019-04-18 2020-10-22 Henkel IP & Holding GmbH Process for preparing cyanoacetates
WO2020212583A1 (en) 2019-04-18 2020-10-22 Henkel IP & Holding GmbH Process for preparing cyanoacetates
WO2020212584A1 (en) 2019-04-18 2020-10-22 Henkel IP & Holding GmbH Process for preparing cyanoacetates
USD907217S1 (en) 2016-09-29 2021-01-05 Ethicon, Inc. Release paper for wound treatment devices
US10993708B2 (en) 2018-07-31 2021-05-04 Ethicon, Inc. Skin closure devices with interrupted closure
WO2021116128A1 (en) 2019-12-12 2021-06-17 Henkel IP & Holding GmbH Process for preparing cyanoacetates
US11504446B2 (en) 2017-04-25 2022-11-22 Ethicon, Inc. Skin closure devices with self-forming exudate drainage channels
EP4209484A1 (en) 2022-07-11 2023-07-12 Aleardis Ltd. Process for preparing electron-deficient olefin monomers
EP4011993A4 (en) * 2019-08-08 2023-07-19 Toagosei Co., Ltd. ADHESIVE COMPOSITION THAT DISINTEGRATES EASILY IN WATER
US11980354B2 (en) 2017-03-23 2024-05-14 Ethicon, Inc. Scaffolds for joining layers of tissue at discrete points
EP4385529A2 (en) 2018-05-02 2024-06-19 Femasys, Inc. Devices for controlled delivery
USD1080864S1 (en) 2020-06-19 2025-06-24 Okapi Medical, Llc Medical adhesive applicator handle

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420293B1 (en) * 1983-05-20 1995-12-06 Toagosei Co., Ltd. Primer
US5057594A (en) * 1989-08-17 1991-10-15 Eastman Kodak Company Ultraviolet light-absorbing compounds and sunscreen formulations and polymeric materials containing such compounds or residues thereof
EP0682651A1 (en) * 1993-01-11 1995-11-22 Eurotax Limited Process for the preparation of esters of 2-cyanoacrylic acid and use of the esters so prepared as adhesives
EP4011863A4 (en) * 2019-08-08 2023-09-20 Toagosei Co., Ltd. 2-cyanoacrylate compound and adhesive composition
JP7563100B2 (ja) * 2020-10-14 2024-10-08 東亞合成株式会社 仮固定用硬化性組成物、及び、仮固定方法
JP7563101B2 (ja) * 2020-10-14 2024-10-08 東亞合成株式会社 剥離性接着物製造用硬化性組成物、剥離性接着物、並びに、剥離方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784215A (en) * 1954-04-07 1957-03-05 Eastman Kodak Co Monomeric esters of alpha-cyanoacrylic acid and their preparation
US3142698A (en) * 1960-10-03 1964-07-28 Borden Co Cyanoacrylate esters
US3465027A (en) * 1965-12-09 1969-09-02 Eastman Kodak Co Process for manufacture of high purity alpha-cyanoacrylates
US3540126A (en) * 1968-07-16 1970-11-17 Minnesota Mining & Mfg Fluoroalkoxyalkyl 2 - cyanoacrylate compositions used in tooth treatment
US3564078A (en) * 1968-05-17 1971-02-16 Eastman Kodak Co Alpha-cyanoacrylate adhesive compositions
US3577394A (en) * 1968-09-27 1971-05-04 Minnesota Mining & Mfg 2-chloroethyl 2-cyanoacrylate and compositions thereof
US3699127A (en) * 1969-10-10 1972-10-17 Loctite Ireland Ltd Plasticized cyanoacrylate adhesive compositions
US3975422A (en) * 1972-11-21 1976-08-17 Johnson & Johnson Preparation of bis (2-cyanoacrylate)monomers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE380011B (Direct) * 1968-06-04 1975-10-27 Minnesota Mining & Mfg
US3559652A (en) * 1968-08-05 1971-02-02 Minnesota Mining & Mfg Method of adhesively repairing body tissue with alkoxyalkyl 2-cyanoacrylate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784215A (en) * 1954-04-07 1957-03-05 Eastman Kodak Co Monomeric esters of alpha-cyanoacrylic acid and their preparation
US3142698A (en) * 1960-10-03 1964-07-28 Borden Co Cyanoacrylate esters
US3465027A (en) * 1965-12-09 1969-09-02 Eastman Kodak Co Process for manufacture of high purity alpha-cyanoacrylates
US3564078A (en) * 1968-05-17 1971-02-16 Eastman Kodak Co Alpha-cyanoacrylate adhesive compositions
US3540126A (en) * 1968-07-16 1970-11-17 Minnesota Mining & Mfg Fluoroalkoxyalkyl 2 - cyanoacrylate compositions used in tooth treatment
US3577394A (en) * 1968-09-27 1971-05-04 Minnesota Mining & Mfg 2-chloroethyl 2-cyanoacrylate and compositions thereof
US3699127A (en) * 1969-10-10 1972-10-17 Loctite Ireland Ltd Plasticized cyanoacrylate adhesive compositions
US3975422A (en) * 1972-11-21 1976-08-17 Johnson & Johnson Preparation of bis (2-cyanoacrylate)monomers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kulkarn; et al., Journal of Applied Polymer Science, vol. 17, pp. 3509-3514, (1973). *

Cited By (174)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675270A (en) * 1986-02-10 1987-06-23 Loctite (Ireland) Limited Imaging method for vapor deposited photoresists of anionically polymerizable monomer
US4986884A (en) * 1986-11-08 1991-01-22 Bayer Aktiengesellschaft Process for the production of monomeric α-cyanoacrylates
US5244968A (en) * 1987-03-19 1993-09-14 The Dow Chemical Company Aqueous-dispersed polymer compositions containing cyanoalkyl esters of unsaturated carboxylic acids
US5877230A (en) * 1991-11-12 1999-03-02 University Of Georgia Research Foundation, Inc. Anionic photoinitiation
US5262200A (en) * 1992-03-27 1993-11-16 Alan Puder System and method of applying cyanoacrylate adhesive activator
US6323275B2 (en) 1992-05-28 2001-11-27 Toagosei Co., Ltd. Cyanoacrylate adhesive composition
US5514372A (en) * 1993-03-31 1996-05-07 Tri-Point Medical L.P. Biocompatible monomer and formaldehyde producing polymer compositions
US5582834A (en) * 1993-03-31 1996-12-10 Tri-Point Medical, Corporation Biocompatible monomer and polymer compositions
US5624669A (en) * 1993-03-31 1997-04-29 Tri-Point Medical Corporation Method of hemostatic sealing of blood vessels and internal organs
US5514371A (en) * 1993-03-31 1996-05-07 Tri-Point Medical L.P. Biocompatible monomer and formaldehyde producing polymer compositions
US5328687A (en) * 1993-03-31 1994-07-12 Tri-Point Medical L.P. Biocompatible monomer and polymer compositions
US5575997A (en) * 1993-03-31 1996-11-19 Tri-Point Medical Corporation Biocompatible monomer and polymer compositions
US6143352A (en) * 1994-06-28 2000-11-07 Closure Medical Corporation pH-modified biocompatible monomer and polymer compositions
US6306243B1 (en) 1994-06-28 2001-10-23 Closure Medical Corporation pH-modified biocompatible monomer and polymer compositions
US6099807A (en) * 1995-06-07 2000-08-08 Closure Medical Corporation Impregnated applicator tip
US7128241B2 (en) 1995-06-07 2006-10-31 Leung Jeffrey C Impregnated applicator tip
US20030063944A1 (en) * 1995-06-07 2003-04-03 Closure Medical Corporation Impregnated applicator tip
US6676322B1 (en) 1995-06-07 2004-01-13 Closure Medical Corporation Impregnated applicator tip
US6376019B1 (en) 1995-06-07 2002-04-23 Closure Medical Corporation Impregnated applicator tip
US20020018689A1 (en) * 1995-06-07 2002-02-14 Badejo Ibraheem T. Adhesive applicators with improved polymerization initiators
US6322852B1 (en) 1995-06-07 2001-11-27 Closure Medical Corporation Impregnated applicator tip
US5928611A (en) * 1995-06-07 1999-07-27 Closure Medical Corporation Impregnated applicator tip
US6010714A (en) * 1996-11-22 2000-01-04 Closure Medical Corporation Non-thermogenic heat dissipating biomedical adhesive compositions
US6433036B1 (en) 1997-02-27 2002-08-13 Loctite Corporation Radiation-curable, cyanoacrylate-containing compositions
US6726795B1 (en) 1997-02-27 2004-04-27 Stan Wojciak Radiation-curable, cyanoacrylate-containing compositions
US6906112B1 (en) 1997-02-27 2005-06-14 Henkel Corporation Radiation-curable, cyanoacrylate-containing compositions
US6217603B1 (en) 1997-08-29 2001-04-17 Closure Medical Corporation Methods of applying monomeric compositions effective as wound closure devices
US6143805A (en) * 1998-02-18 2000-11-07 Closure Medical Corporation Electron beam sterilization of liquid adhesive compositions
US6174919B1 (en) 1998-02-18 2001-01-16 Closure Medical Corporation Cyanoacrylate compositions with vinyl terminated ester groups
US20040137067A1 (en) * 1998-04-30 2004-07-15 Closure Medical Corporation Adhesive applicator tip with a polymerization initiator, polymerization rate modifier, and/or bioactive material
US6455064B1 (en) 1998-04-30 2002-09-24 Closure Medical Corporation Method of applying an adhesive composition over a bioactive polymerization initiator or accelerator
US6512023B1 (en) 1998-06-18 2003-01-28 Closure Medical Corporation Stabilized monomer adhesive compositions
US20050042197A1 (en) * 1998-11-12 2005-02-24 Shalaby Shalaby W. Stabilized polyester/cyanoacrylate tissue adhesive formulation
US6595940B1 (en) 1998-12-23 2003-07-22 Closure Medical Corporation Applicator for dispensable liquids
US6283933B1 (en) 1998-12-23 2001-09-04 Closure Medical Corporation Applicator for dispensable liquids
US6352704B1 (en) 1999-06-30 2002-03-05 Closure Medical Corporation Flavored cyanoacrylate compositions
US6433096B1 (en) 1999-08-12 2002-08-13 Closure Medical Corporation Sterilized cyanoacrylate solutions containing thickeners
US6743858B2 (en) 1999-08-12 2004-06-01 Closure Medical Corporation Sterilized cyanoacrylate solutions containing thickeners
US6310166B1 (en) 1999-08-12 2001-10-30 Closure Medical Corporation Sterilized cyanoacrylate solutions containing thickeners
US6245933B1 (en) 1999-11-19 2001-06-12 Closure Medical Corporation Transesterification method for making cyanoacrylates
WO2001036380A3 (en) * 1999-11-19 2001-12-13 Closure Medical Corp Transesterification method for making cyanoacrylates
US6488944B2 (en) 1999-12-23 2002-12-03 Closure Medical Corporation 1, 1-disubstituted ethylene adhesive compositions containing polydimethylsiloxane
US6183593B1 (en) 1999-12-23 2001-02-06 Closure Medical Corporation 1,1-disubstituted ethylene adhesive compositions containing polydimethylsiloxane
US6428234B1 (en) 2000-01-07 2002-08-06 Closure Medical Corporation Adhesive applicator tips with improved flow properties
US6592281B2 (en) 2000-01-07 2003-07-15 Closure Medical Corporation Adhesive applicator tips with improved flow properties
US6637967B2 (en) 2000-01-07 2003-10-28 Closure Medical Corporation Adhesive applicator tips with improved flow properties
US6425704B2 (en) 2000-01-07 2002-07-30 Closure Medical Corporation Adhesive applicators with improved applicator tips
US6428233B1 (en) 2000-01-07 2002-08-06 Closure Medical Corporation Adhesive applicator tips with improved flow properties
US6705790B2 (en) 2000-01-07 2004-03-16 Closure Medical Corporation Adhesive applicators with improved applicator tips
US6605667B1 (en) 2000-09-08 2003-08-12 Closure Medical Corporation Antioxidant enriched adhesive compositions and storage containers therefor
US6607631B1 (en) 2000-09-08 2003-08-19 Closure Medical Corporation Adhesive compositions with reduced coefficient of friction
WO2002053666A1 (en) * 2001-01-08 2002-07-11 Loctite (R & D) Limited Cyanoacrylate compositions curable to flexible polymeric materials
US6977278B1 (en) 2001-01-08 2005-12-20 Loctite (R&D) Ltd. Cyanoacrylate compositions curable to flexible polymeric materials
KR100810836B1 (ko) 2001-01-08 2008-03-06 록타이트(알 앤 디) 리미티드 가요성 중합체 물질로 경화될 수 있는 시아노아크릴레이트조성물
US6748950B2 (en) 2001-04-30 2004-06-15 Closure Medical Corporation Compositions and medical procedure to treat snoring
US6779657B2 (en) 2001-06-06 2004-08-24 Closure Medical Corporation Single-use applicators, dispensers and methods for polymerizable monomer compound
US6616019B2 (en) 2001-07-18 2003-09-09 Closure Medical Corporation Adhesive applicator with improved applicator tip
US6811341B2 (en) 2001-08-16 2004-11-02 Closure Medical Corporation Multiple-component combining
US6547467B2 (en) 2001-08-29 2003-04-15 Closure Medical Corporation Microapplicators, delivery systems and methods for adhesives and sealants
US6660327B2 (en) 2001-12-28 2003-12-09 Mattel, Inc. Process of applying a cyanoadhesive composition
US7001947B2 (en) 2001-12-28 2006-02-21 Mattel, Inc. Cyanoadhesive composition for toy articles
US20040151688A1 (en) * 2003-01-31 2004-08-05 Closure Medical Corporation Adhesive treatment for epistaxis
EP2363209A2 (en) 2003-02-07 2011-09-07 Ethicon, Inc. Applicators, dispensers and methods for dispensing and applying adhesive material
US8790032B2 (en) 2003-02-07 2014-07-29 Ethicon, Inc. Applicators, dispensers and methods for dispensing and applying adhesive material
US20040223946A1 (en) * 2003-05-05 2004-11-11 Closure Medical Corporation Adhesive treatment for insect and related bites
US20040223932A1 (en) * 2003-05-05 2004-11-11 Closure Medical Corporation Adhesive treatment for acne
US20050042266A1 (en) * 2003-08-21 2005-02-24 Closure Medical Corporation Cyanoacrylate compositions containing anti-microbial agent
US8337881B2 (en) 2003-09-08 2012-12-25 Ethicon, Inc. Cyanoacrylate monomer formulation containing diiodomethyl-p-tolylsulfone
US20050182443A1 (en) * 2004-02-18 2005-08-18 Closure Medical Corporation Adhesive-containing wound closure device and method
EP2762086A1 (en) 2004-02-18 2014-08-06 Ethicon Inc. Adhesive-containing wound closure device
US9655622B2 (en) 2004-02-18 2017-05-23 Ethicon, Inc. Adhesive-containing wound closure device and method
US11413370B2 (en) 2004-02-18 2022-08-16 Ethicon, Inc. Adhesive-containing wound closure device and method
US10398802B2 (en) 2004-02-18 2019-09-03 Ethicon, Inc. Adhesive-containing wound closure device and method
US10434211B2 (en) 2004-02-18 2019-10-08 Ethicon, Inc. Adhesive-containing wound closure device and method
US10398800B2 (en) 2004-07-12 2019-09-03 Ethicon, Inc. Adhesive-containing wound closure device and method
US20080255610A1 (en) * 2004-07-12 2008-10-16 Closure Medical Corporation Adhesive-Containing Wound Closure Device and Method
US11446407B2 (en) 2004-07-12 2022-09-20 Ethicon, Inc. Adhesive-containing wound closure device and method
US9623142B2 (en) 2004-07-12 2017-04-18 Ethicon, Inc. Adhesive-containing wound closure device and method
US20060009099A1 (en) * 2004-07-12 2006-01-12 Closure Medical Corporation Adhesive-containing wound closure device and method
US20070078207A1 (en) * 2005-09-30 2007-04-05 Jonn Jerry Y Stabilizer cyanoacrylate formulations
US20070213553A1 (en) * 2006-03-10 2007-09-13 Hongbo Liu Method for producing a cyanoacrylate monomer
US7659423B1 (en) 2006-04-18 2010-02-09 Loctite (R&D) Limited Method of preparing electron deficient olefins in polar solvents
US20080003196A1 (en) * 2006-06-30 2008-01-03 Jonn Jerry Y Absorbable cyanoacrylate compositions
US20100047433A1 (en) * 2006-10-06 2010-02-25 Toagosei Co., Ltd Polymer for detecting fingerprint, method of producing the same, composition for detecting fingerprint and method of detecting fingerprint using the same
US8268919B2 (en) * 2006-10-06 2012-09-18 Toagosei Co., Ltd. Polymer for detecting fingerprint, method of producing the same, composition for detecting fingerprint and method of detecting fingerprint using the same
US8022251B2 (en) 2006-10-25 2011-09-20 Loctite (R&D) Limited Iminium salts and methods of preparing electron deficient olefins using such novel iminium salts
US7569719B1 (en) 2006-10-25 2009-08-04 Loctite (R&D) Limited Method of preparing electron deficient olefins
US20090203934A1 (en) * 2006-10-25 2009-08-13 Loctite (R&D) Limited Novel iminium salts and methods of preparing electron deficient olefins using such novel iminium salts
US8287202B2 (en) 2006-11-30 2012-10-16 Ethicon, Inc. Method for dispensing a polymerizable monomer adhesive
US8118508B2 (en) 2006-11-30 2012-02-21 Closure Medical Corporation Dispenser with a frangible container and a rotating breaking member, for dispensing a polymerizable monomer adhesive
WO2008067220A2 (en) 2006-11-30 2008-06-05 Closure Medical Corporation Dispenser
US20080131190A1 (en) * 2006-11-30 2008-06-05 Jack Goodman Dispenser
US7718821B1 (en) 2006-12-19 2010-05-18 Loctite (R&D) Limited Method of preparing electron deficient olefins
US8729121B2 (en) 2007-06-25 2014-05-20 Adhezion Biomedical, Llc Curing accelerator and method of making
US9018254B2 (en) 2007-06-25 2015-04-28 Adhezion Biomedical, Llc Cyanoacrylate tissue adhesives with desirable permeability and tensile strength
US8980947B2 (en) 2007-06-25 2015-03-17 Adhezion Biomedical, Llc Curing accelerator and method of making
US20100210788A1 (en) * 2007-10-24 2010-08-19 Loctite (R&D) Limited Electron deficient olefins
US8053589B1 (en) 2007-10-24 2011-11-08 Henkel Ireland Limited Imines and methods of preparing electron deficient olefins using such novel imines
US7973119B1 (en) 2007-10-24 2011-07-05 Loctite (R&D) Limited Adhesive systems using imines and salts thereof and precursurs to electron deficient olefins
US20100199888A1 (en) * 2007-10-24 2010-08-12 Loctite (R&D) Limited Activated methylene reagents and curable compositions prepared therefrom
US8481755B2 (en) 2007-10-24 2013-07-09 Henkel Ireland Ltd. Activated methylene reagents and curable compositions prepared therefrom
US9481640B2 (en) 2007-10-24 2016-11-01 Henkel IP & Holding GmbH Electron deficient olefins
US8613952B2 (en) 2007-11-14 2013-12-24 Adhezion Biomedical, Llc Cyanoacrylate tissue adhesives
US9878041B2 (en) 2007-11-14 2018-01-30 Adhezion Biomedical, Llc Cyanoacrylate tissue adhesives
EP2116126A1 (en) 2008-05-06 2009-11-11 Henkel AG & Co. KGaA Method and apparatus for grafting plants with fast-curing adhesives
US8603451B2 (en) 2008-06-20 2013-12-10 Adhezion Biomedical, Llc Adhesive compositions for medical use: single additive as both the thickening agent and the accelerator
EP2679251A1 (en) 2008-06-20 2014-01-01 Adhezion Biomedical, LLC Adhesive compositions for medical use: single additive as both the thickening agent and the accelerator
US8293838B2 (en) 2008-06-20 2012-10-23 Adhezion Biomedical, Llc Stable and sterile tissue adhesive composition with a controlled high viscosity
US8198344B2 (en) 2008-06-20 2012-06-12 Adhezion Biomedical, Llc Method of preparing adhesive compositions for medical use: single additive as both the thickening agent and the accelerator
US7932305B2 (en) 2008-06-27 2011-04-26 Ethicon, Inc. Viscous α-cyanoacrylate compositions
US20100030258A1 (en) * 2008-07-31 2010-02-04 Badejo Ibraheem T Controlled Exotherm of Cyanoacrylate Formulations
US8153743B2 (en) 2008-07-31 2012-04-10 Closure Medical Corporation Controlled exotherm of cyanoacrylate formulations
US8399698B1 (en) 2008-10-24 2013-03-19 Henkel Ireland Limited Substituted activated methylene reagents and methods of using such reagents to form electron deficient olefins
US10196471B1 (en) 2008-10-24 2019-02-05 Henkel IP & Holding GmbH Curable composition having an electron deficient olefin
US8652510B2 (en) 2008-10-31 2014-02-18 Adhezion Biomedical, Llc Sterilized liquid compositions of cyanoacrylate monomer mixtures
US9254133B2 (en) 2008-10-31 2016-02-09 Adhezion Biomedical, Llc Sterilized liquid compositions of cyanoacrylate monomer mixtures
US8609128B2 (en) 2008-10-31 2013-12-17 Adhezion Biomedical, Llc Cyanoacrylate-based liquid microbial sealant drape
US20110230561A1 (en) * 2008-11-25 2011-09-22 Hongbo Liu Medical adhesive compositions
WO2011008374A2 (en) 2009-06-30 2011-01-20 Ethicon, Inc. A cyanoacrylate initiator system
US20100330027A1 (en) * 2009-06-30 2010-12-30 Hongbo Liu Cyanoacrylate Initiator System
US8475825B2 (en) 2009-06-30 2013-07-02 Ethicon, Inc. Cyanoacrylate initiator system
US9309019B2 (en) 2010-05-21 2016-04-12 Adhezion Biomedical, Llc Low dose gamma sterilization of liquid adhesives
US8932623B2 (en) 2011-08-25 2015-01-13 Ethicon, Inc. Protective wound dressing device for oral and pharyngeal space
WO2013028672A1 (en) 2011-08-25 2013-02-28 Ethicon, Inc. Protective wound dressing device for oral and pharyngeal space
WO2014172519A1 (en) 2013-04-19 2014-10-23 Adhezion Biomedical, Llc Package system for sterilizing and storing cyanoacrylate adhesive compositions
CN103232366A (zh) * 2013-04-25 2013-08-07 华南理工大学 一种α-氰基丙烯酸-2-甲氧基乙酯的制备方法
US9528034B2 (en) 2013-05-21 2016-12-27 Henkel IP & Holding GmbH Cyanoacrylate compositions
US10196316B2 (en) 2013-12-05 2019-02-05 Toagosei Co., Ltd. Reinforcement method for three-dimensional shaped object
US9421297B2 (en) 2014-04-02 2016-08-23 Adhezion Biomedical, Llc Sterilized compositions of cyanoacrylate monomers and naphthoquinone 2,3-oxides
WO2016038514A1 (en) 2014-09-12 2016-03-17 Afinitica Technologies, S. L. Fast and elastic adhesive
EP2995663A1 (en) 2014-09-12 2016-03-16 Afinitica Technologies, S. L. Fast and elastic adhesive
USD824525S1 (en) 2014-09-25 2018-07-31 Ethicon Llc Release paper for wound treament devices
USD854171S1 (en) 2014-09-25 2019-07-16 Ethicon Llc Release paper for wound treatment devices
US9839717B2 (en) 2015-09-10 2017-12-12 Fa-Ter CHU Cyanoacrylate adhesive composition and method for making the same
US10792024B2 (en) 2016-09-28 2020-10-06 Ethicon, Inc. Scaffolds with channels for joining layers of tissue at discrete points
US10687986B2 (en) 2016-09-29 2020-06-23 Ethicon, Inc. Methods and devices for skin closure
US12403043B2 (en) 2016-09-29 2025-09-02 Ethicon, Inc. Methods and devices for skin closure
USD907217S1 (en) 2016-09-29 2021-01-05 Ethicon, Inc. Release paper for wound treatment devices
US11679034B2 (en) 2016-09-29 2023-06-20 Ethicon, Inc. Methods and devices for skin closure
USD979768S1 (en) 2016-09-29 2023-02-28 Ethicon, Inc. Release paper for wound treatment devices
US10470934B2 (en) 2016-09-29 2019-11-12 Ethicon, Inc. Methods and devices for skin closure
WO2018114463A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefin precursors
WO2018114464A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
WO2018114460A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
WO2018114457A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefin precursors
WO2018114458A1 (en) 2016-12-23 2018-06-28 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
US10822303B2 (en) 2016-12-23 2020-11-03 Henkel IP & Holding GmbH Process for preparing electron deficient olefin precursors
US10927071B2 (en) 2016-12-23 2021-02-23 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
US10889542B2 (en) 2016-12-23 2021-01-12 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
US10913708B2 (en) 2016-12-23 2021-02-09 Henkel IP & Holding GmbH Process for preparing electron deficient olefin precursors
US10913707B2 (en) 2016-12-23 2021-02-09 Henkel IP & Holding GmbH Process for preparing electron deficient olefins
US10988274B2 (en) 2017-02-07 2021-04-27 Adhezion Biomedical, Llc Packaging for adhesive compositions
WO2018148057A1 (en) 2017-02-07 2018-08-16 Adhezion Biomedical, Llc Packaging for adhesive compositions, method for sterilizing
EP4613213A2 (en) 2017-02-09 2025-09-10 Femasys, Inc. Methods and compositions comprising biodegradable cyanoacrylates for medical applications
WO2018148453A1 (en) 2017-02-09 2018-08-16 Femasys, Inc. Methods and compositions comprising biodegradable cyanoacrylates
US11883264B2 (en) 2017-03-23 2024-01-30 Ethicon, Inc. Skin closure systems and devices of improved flexibility and stretchability for bendable joints
US10470935B2 (en) 2017-03-23 2019-11-12 Ethicon, Inc. Skin closure systems and devices of improved flexibility and stretchability for bendable joints
US11980354B2 (en) 2017-03-23 2024-05-14 Ethicon, Inc. Scaffolds for joining layers of tissue at discrete points
US11504446B2 (en) 2017-04-25 2022-11-22 Ethicon, Inc. Skin closure devices with self-forming exudate drainage channels
EP4385529A2 (en) 2018-05-02 2024-06-19 Femasys, Inc. Devices for controlled delivery
US10993708B2 (en) 2018-07-31 2021-05-04 Ethicon, Inc. Skin closure devices with interrupted closure
US11974734B2 (en) 2018-07-31 2024-05-07 Ethicon, Inc. Skin closure devices with interrupted closure
WO2020212584A1 (en) 2019-04-18 2020-10-22 Henkel IP & Holding GmbH Process for preparing cyanoacetates
US11827584B2 (en) 2019-04-18 2023-11-28 Henkel Ag & Co. Kgaa Process for preparing cyanoacetates
WO2020212583A1 (en) 2019-04-18 2020-10-22 Henkel IP & Holding GmbH Process for preparing cyanoacetates
US12351540B2 (en) 2019-04-18 2025-07-08 Henkel Ag & Co. Kgaa Process for preparing cyanoacetates
WO2020212585A1 (en) 2019-04-18 2020-10-22 Henkel IP & Holding GmbH Process for preparing cyanoacetates
EP4011993A4 (en) * 2019-08-08 2023-07-19 Toagosei Co., Ltd. ADHESIVE COMPOSITION THAT DISINTEGRATES EASILY IN WATER
US11976024B2 (en) 2019-12-12 2024-05-07 Henkel Ag & Co. Kgaa Process for preparing cyanoacetates
WO2021116128A1 (en) 2019-12-12 2021-06-17 Henkel IP & Holding GmbH Process for preparing cyanoacetates
USD1080864S1 (en) 2020-06-19 2025-06-24 Okapi Medical, Llc Medical adhesive applicator handle
USD1080863S1 (en) 2020-06-19 2025-06-24 Okapi Medical, Llc Medical adhesive applicator body
WO2023131729A1 (en) 2022-07-11 2023-07-13 Aeardis Ltd. Process for preparing electron-deficient olefin monomers
EP4209484A1 (en) 2022-07-11 2023-07-12 Aleardis Ltd. Process for preparing electron-deficient olefin monomers

Also Published As

Publication number Publication date
FR2479208A1 (fr) 1981-10-02
IE810571L (en) 1981-09-27
JPS6113702B2 (Direct) 1986-04-15
GB2073183A (en) 1981-10-14
FR2479208B1 (fr) 1985-08-16
MX157722A (es) 1988-12-13
CA1161062A (en) 1984-01-24
IE51033B1 (en) 1986-09-17
GB2073183B (en) 1984-06-20
JPS56135455A (en) 1981-10-22
DE3111974A1 (de) 1982-02-18

Similar Documents

Publication Publication Date Title
US4364876A (en) Novel 2-cyanoacrylate, process for producing same and curable composition comprising same
US5140084A (en) Silicon-containing alpha-cyanoacrylates
US10526426B2 (en) Photoinitiators that are polymeric or polymerizable for use in UV curable pressure sensitive adhesives
US5290838A (en) α-cyanoacrylate containing adhesive composition
CA1152096A (en) Polymerisable composition and acrylates and methacrylates
US4755623A (en) Polyfunctional amine crosslinker, process for making same, and compositions containing same
WO2002046291A1 (en) Multi-functional alpha-alkoxyalkyl acrylate and methacrylate ester compositions and reworkable polymers formed therefrom
US5276069A (en) Contact adhesives for self-adhesive articles
US6231714B1 (en) Allylic phenyl ether (meth)acrylate compositions and novel allylic phenyl ether (meth)acrylate monomers
US4886618A (en) Aldehyde or imine oxygen scavengers for vinyl polymerizations
US6627762B1 (en) Acetal and hemiacetal ester linked propylene carbonate functional (meth)acrylic esters and method of making same
KR0152388B1 (ko) N-비닐포름아미드와 아크릴 및 메트아크릴 에스테르의 마이클 부가반응 생성물
JP7259968B2 (ja) ２－シアノアクリレート化合物、及び、接着剤組成物
KR850001087B1 (ko) 2-시아노아크릴레이트의 제조방법
KR20010106459A (ko) 브롬화 재료
US3924043A (en) Pressure sensitive adhesives of polymers of cycloaliphatic and phenylalkyl acrylates and vinyl esters
US4788321A (en) Perfluoroalkenyloxybenzoic acid derivative, process for preparing the same and prepolymer of the derivative
JPH06192202A (ja) ２−シアノアクリレート
Bogaert et al. Reactive polymers containing pendant azetidine or azetidinium functions, 1. Synthesis of poly (acrylic ester) s and poly (methacrylic ester) s of 1‐alkyl‐3‐hydroxyazetidines and related azetidinium salts
CA1226092A (en) Anaerobic adhesives containing polymerizable activators activators
JPS6410535B2 (Direct)
CA1240339A (en) Polyfunctional amine crosslinker, process for making same, and compositions containing same
JPH06128212A (ja) ２−シアノアクリレート
JPS614710A (ja) 重合しうる活性化剤を含む嫌気性接着剤
JPH0859590A (ja) アクリロニトリル二量体、アクリロニトリル誘導体、それらの製造方法および重合性組成物

Legal Events

Date Code Title Description
AS Assignment

Owner name: TOAGOSEI CHEMICAL INDUSTRY CO.,LTD., 14-1, NISHI S

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KIMURA KAORU;SAKABE KAZUYUKI;REEL/FRAME:003872/0667

Effective date: 19810303

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M171); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M185); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12